CN108560016A - A kind of synthetic method of polysubstituted allyl carboxylic acid compound - Google Patents
A kind of synthetic method of polysubstituted allyl carboxylic acid compound Download PDFInfo
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- CN108560016A CN108560016A CN201810605790.4A CN201810605790A CN108560016A CN 108560016 A CN108560016 A CN 108560016A CN 201810605790 A CN201810605790 A CN 201810605790A CN 108560016 A CN108560016 A CN 108560016A
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- carboxylic acid
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Abstract
The present invention discloses a kind of synthetic method of polysubstituted allyl carboxylic acid compound, and reaction formula is as follows：
Description
Technical field
The invention belongs to technical field of organic synthesis, and in particular to a kind of synthesis of polysubstituted allyl carboxylic acid compound
Method.
Technical background
Polysubstituted allyl yl carboxylic acid is a kind of important organic molecule, is had extensively in chemical raw material and drug etc.
Application value.Therefore, the synthetic method of polysubstituted allyl yl carboxylic acid becomes the concern place of people.In recent years, people is studied
Transition metal-catalyzed synthesis strategy of the member under sustainable development idea guiding, develops several synthetic methods, such as：Benzene second
Vinyl compound in the presence of diethyl zinc and carbon dioxide carboxylation reaction of hydrogen (J.Am.Chem.Soc.2008,130,
14936.), this method has the shortcomings that diethyl zinc amount of reagent is big；The asymmetric cyclisation carboxylated of 1,5- biconjugate diene
It reacts (J.Am.Chem.Soc.2004,126,5956), this method has the shortcomings that need special substrate, these are all limited
The application of synthetic method.Therefore the synthetic method for developing efficient, highly selective polysubstituted allyl yl carboxylic acid is imperative.
Invention content
It is an object of the invention to overcome the defect of existing technology of preparing, provide it is a kind of it is highly selective, reaction condition is mild,
The good feature of environmental-friendly, high income, purity is suitable for the conjunction of the polysubstituted allyl carboxylic acid compound of industrialized production
At method.
For this purpose, the technical scheme is that：
A kind of synthetic method of polysubstituted allyl carboxylic acid compound, which is characterized in that electrolysis is added in a cell
Polysubstituted allyl yl carboxylic acid acetate, catalyst, ligand, solvent is added in the super dry DMF solution of matter, in carbon dioxide gas stream
Lower electrolysis 3-6h obtains polysubstituted allyl carboxylic acid compound after dilute hydrochloric acid acidification, reacts as shown in reaction equation 1：
Formula 1
Wherein：
(1) R, R1For C6~C30(miscellaneous) aryl；
(2) R, R2For H；
(3) R, R3For H or C1~C30Alkyl；
(4) R, R4For H or C1~C30Alkyl；
(5) R, R5For H or C1~C30Alkyl.
2. selected electrolyte is Et in the above scheme4NOTs、Bu4NOTs、Me4NOTs、Pr4NOTs、Bu4NCl、
Bu4NBr、Bu4NI、Bu4NBF4、Bu4NClO4One of in.
3. selected catalyst is palladium, trifluoracetic acid palladium, palladium bichloride, palladium bromide, bi triphenyl in the above scheme
One of in phosphine dichloride palladium, palladium acetylacetonate, palladium oxide, hexafluoroacetylacetone palladium.
4. in the above scheme selected ligand be in DPPPh, DPPF, DPPE, DPPM, DPPP, DPPB wherein it
One.
5. selected solvent is DMF, DMSO, MeCN, MeOH, EtOH, HOAc, H in the above scheme2O、 THF、
One or both of Toluene is combined.
6. selected anode electrolytic cell electrode is magnesium sheet electrode in the above scheme, cathode electrode is platinum plate electrode.
7. selected Faradaic current is 5~15mA in the above scheme.
8. a concentration of 1mol/L of selected dilute hydrochloric acid in the above scheme.
Compared with prior art, the present invention provide technical solution by the super dry DMF solution of electrolyte, be added catalyst, match
Body, substrate, solution are added in electrolytic cell, and polysubstituted allyl carboxylic acid compound is obtained by the reaction, which has height
Selectivity, the feature that reaction condition is mild, environmental-friendly, high income, purity are good.Therefore the present invention has good practical value,
There is good reference to the exploitation of polysubstituted allyl carboxylic acid compound Product Process.
Specific implementation mode
Below by way of specific embodiment, the present invention is described further, but it is above-mentioned that this should not be interpreted as to the present invention
The range of theme is only limitted to embodiment below, and all technologies realized based on the above of the present invention belong to the model of the present invention
It encloses.
Embodiment 1
In 10mL hydrogenates pipe electrolytic cell, positive (Mg)/negative (Pt) (1.0x 1.0cm are filled2) electrode, lead to carbon dioxide discharge
The super dry DMF solution (0.15g/6.0mL) of tetraethyl paratoluenesulfonic acid ammonium salt is added after air, after the drying of promoting menstruation concentrated sulfuric acid solution
Carbon dioxide 30 minutes, palladium (0.015mmol, 3.4mg, 5mol%), ligand 1, the bis- diphenylphosphine benzene of 2- are added afterwards
(0.016 mmol, 7.2mg, 5.3mol%), substrate 1a (0.3mmol, 76.5mg, 1.0equiv) and ethyl alcohol (0.3mmol,
17.5uL, 1.0equiv), connection electrode, setting electric current is 8mA, is powered, and after being electrolysed 3h under carbon dioxide gas stream, closes electricity
Source.The dilute hydrochloric acid of 1M is acidified, and isometric ethyl acetate extracts 3 times, and organic phase is washed 4 times with saturated ammonium chloride, and anhydrous sodium sulfate is dry
Dry, concentration, rapid column chromatography purifies to obtain target product 2a (colourless oil liquid, 58.6mg, yield 81%).
Product testing data are as follows：1H NMR(400MHz,CDCl3) δ 7.47 (d, J=8.4Hz, 2H), 7.20 (d, J=
8.4Hz, 2H), 6.25-6.07 (m, 1H), 5.28 (t, J=7.9Hz, 1H), 5.19 (d, J=17.1Hz, 1H), 4.29 (d, J=
7.8Hz,1H).13C NMR(101MHz,CDCl3)δ178.17,136.22,134.31,131.89,129.87,121.73,
118.61,54.84.HRMS(EI)calcd for C10H9O2Br:239.9786,found:239.9794.
Embodiment 2
In 10mL hydrogenates pipe electrolytic cell, positive (Mg)/negative (Pt) (1.0x 1.0cm are filled2) electrode, lead to carbon dioxide discharge
The super dry DMF solution (0.15g/6.0mL) of tetraethyl paratoluenesulfonic acid ammonium salt is added after air, after the drying of promoting menstruation concentrated sulfuric acid solution
Carbon dioxide 30 minutes, palladium (0.015mmol, 3.4mg, 5mol%), ligand 1, the bis- diphenylphosphine benzene of 2- are added afterwards
(0.016 mmol, 7.2mg, 5.3mol%), substrate 1b (0.3mmol, 52.8mg, 1.0equiv) and ethyl alcohol (0.3mmol,
17.5uL, 1.0equiv), connection electrode, setting electric current is 8mA, is powered, and after being electrolysed 3h under carbon dioxide gas stream, closes electricity
Source.The dilute hydrochloric acid of 1M is acidified, and isometric ethyl acetate extracts 3 times, and organic phase is washed 4 times with saturated ammonium chloride, and anhydrous sodium sulfate is dry
Dry, concentration, rapid column chromatography purifies to obtain target product 2b (pale yellowish oil liquid, 28.2mg, yield 58%).
Product testing data are as follows：1H NMR(400MHz,CDCl3)δ7.45–7.27(m,5H),6.38–6.17(m,1H),
5.28 (d, J=10.2Hz, 1H), 5.23 (d, J=17.1Hz, 1H), 4.37 (d, J=8.0Hz, 1H)13C NMR(101 MHz,
CDCl3)δ178.80,137.37,134.97,128.83,128.12,127.65,118.13,55.59.HRMS (ESI-TOF)
calcd for C10H11O2[M+H]+:163.0754,found:163.0754.
Embodiment 3
In 10mL hydrogenates pipe electrolytic cell, positive (Mg)/negative (Pt) (1.0x 1.0cm2) electrode is filled, carbon dioxide discharge is led to
The super dry DMF solution (0.15g/6.0mL) of tetraethyl paratoluenesulfonic acid ammonium salt is added after air, after the drying of promoting menstruation concentrated sulfuric acid solution
Carbon dioxide 30 minutes, palladium (0.015mmol, 3.4mg, 5mol%), ligand 1, the bis- diphenylphosphine benzene of 2- are added afterwards
(0.016mmol, 7.2mg, 5.3mol%), substrate 1c (0.3mmol, 57.1mg, 1.0equiv) and ethyl alcohol (0.3mmol,
17.5uL, 1.0equiv), connection electrode, setting electric current is 8mA, is powered, and after being electrolysed 3h under carbon dioxide gas stream, closes electricity
Source.The dilute hydrochloric acid of 1M is acidified, and isometric ethyl acetate extracts 3 times, and organic phase is washed 4 times with saturated ammonium chloride, and anhydrous sodium sulfate is dry
Dry, concentration, rapid column chromatography purifies to obtain target product 2c (white solid, 35.0mg, yield 65%).
Product testing data are as follows：1H NMR(400MHz,CDCl3) δ 7.21 (d, J=8.0Hz, 1H), 7.15 (d, J=
7.9Hz, 1H), 6.28-6.12 (m, 1H), 5.23 (d, J=10.2Hz, 1H), 5.17 (d, J=17.7Hz, 1H), 4.29 (d, J
=8.0Hz, 1H), 2.33 (s, 1H)13C NMR(101MHz,CDCl3)δ178.79,137.33,135.10,134.38,
129.47,127.92,117.85,55.11,21.05.HRMS(ESI-TOF)calcd for C11H113O2[M+H]+:
177.0910, found:177.0910.
Embodiment 4
In 10mL hydrogenates pipe electrolytic cell, positive (Mg)/negative (Pt) (1.0x 1.0cm2) electrode is filled, carbon dioxide discharge is led to
The super dry DMF solution (0.15g/6.0mL) of tetraethyl paratoluenesulfonic acid ammonium salt is added after air, after the drying of promoting menstruation concentrated sulfuric acid solution
Carbon dioxide 30 minutes, palladium (0.015mmol, 3.4mg, 5mol%), ligand 1, the bis- diphenylphosphine benzene of 2- are added afterwards
(0.016mmol, 7.2mg, 5.3mol%), substrate 1d (0.3mmol, 61.9mg, 1.0equiv) and ethyl alcohol (0.3mmol,
17.5uL, 1.0equiv), connection electrode, setting electric current is 8mA, is powered, and after being electrolysed 3h under carbon dioxide gas stream, closes electricity
Source.The dilute hydrochloric acid of 1M is acidified, and isometric ethyl acetate extracts 3 times, and organic phase is washed 4 times with saturated ammonium chloride, and anhydrous sodium sulfate is dry
Dry, concentration, rapid column chromatography purifies to obtain target product 2d (pale yellowish oil liquid, 36.0mg, yield 62%).
Product testing data are as follows：1H NMR(400MHz,CDCl3) δ 7.24 (d, J=8.7Hz, 1H), 6.88 (d, J=
8.6Hz, 1H), 6.31-6.09 (m, 1H), 5.23 (d, J=10.2Hz, 1H), 5.17 (d, J=17.1Hz, 1H), 4.28 (d, J
=7.9Hz, 1H), 3.80 (s, 1H)13C NMR(101MHz,CDCl3)δ178.71,158.99,135.16,129.43,
129.16,117.79,114.17,55.28,54.63.HRMS(ESI-TOF)calcd for C11H13O3[M+H]+:
193.0859, found:193.0860.
Embodiment 5
In 10mL hydrogenates pipe electrolytic cell, positive (Mg)/negative (Pt) (1.0x 1.0cm2) electrode is filled, carbon dioxide discharge is led to
The super dry DMF solution (0.15g/6.0mL) of tetraethyl paratoluenesulfonic acid ammonium salt is added after air, after the drying of promoting menstruation concentrated sulfuric acid solution
Carbon dioxide 30 minutes, palladium (0.015mmol, 3.4mg, 5mol%), ligand 1, the bis- diphenylphosphine benzene of 2- are added afterwards
(0.016mmol, 7.2mg, 5.3mol%), substrate 1e (0.3mmol, 69.7mg, 1.0equiv) and ethyl alcohol (0.3mmol,
17.5uL, 1.0equiv), connection electrode, setting electric current is 8mA, is powered, and after being electrolysed 3h under carbon dioxide gas stream, closes electricity
Source.The dilute hydrochloric acid of 1M is acidified, and isometric ethyl acetate extracts 3 times, and organic phase is washed 4 times with saturated ammonium chloride, and anhydrous sodium sulfate is dry
Dry, concentration, rapid column chromatography purifies to obtain target product 2e (yellow solid, 52.4mg, yield 80%).
Product testing data are as follows：1H NMR(400MHz,CDCl3) δ 7.39 (d, J=8.3Hz, 2H), 7.29 (d, J=
8.3Hz, 2H), 6.31-6.15 (m, 1H), 5.31-5.18 (m, 2H), 4.33 (d, J=8.2Hz, 1H), 1.34 (s, 9H)13C
NMR(101MHz,CDCl3)δ179.00,150.51,135.10,134.32,127.67,125.75,117.88,55.18,
34.50,31.33.HRMS(ESI-TOF)calcd for C14H19O2[M+H]+:219.1380,found:219.1381。
Claims (8)
1. a kind of synthetic method of polysubstituted allyl carboxylic acid compound, which is characterized in that electrolyte is added in a cell
Super dry DMF solution, polysubstituted allyl yl carboxylic acid acetate, catalyst, ligand, solution is added, it is electric under carbon dioxide gas stream
3-6h is solved, polysubstituted allyl carboxylic acid compound is obtained after dilute hydrochloric acid acidification, reacts as shown in reaction equation 1：
Wherein：
(1) R, R1For C6~C30(miscellaneous) aryl；
(2) R, R2For H；
(3) R, R3For H or C1~C30Alkyl；
(4) R, R4For H or C1~C30Alkyl；
(5) R, R5For H or C1~C30Alkyl.
2. the synthetic method of polysubstituted allyl carboxylic acid compound according to claim 1, which is characterized in that described
Electrolyte be Et4NOTs、Bu4NOTs、Me4NOTs、Pr4NOTs、Bu4NCl、Bu4NBr、Bu4NI、Bu4NBF4、Bu4NClO4In
One of.
3. the synthetic method of polysubstituted allyl carboxylic acid compound according to claim 1, which is characterized in that described
Catalyst be palladium, trifluoracetic acid palladium, palladium bichloride, palladium bromide, bis-triphenylphosphipalladium palladium dichloride, palladium acetylacetonate, oxidation
One of in palladium, hexafluoroacetylacetone palladium.
4. the synthetic method of polysubstituted allyl carboxylic acid compound according to claim 1, which is characterized in that described
Ligand be DPPPh, DPPF, DPPE, DPPM, DPPP, DPPB in one of.
5. the synthetic method of polysubstituted allyl carboxylic acid compound according to claim 1, which is characterized in that described
Solvent be DMF, DMSO, MeCN, MeOH, EtOH, HOAc, H2O, one or both of THF, Toluene are combined.
6. the synthetic method of polysubstituted allyl carboxylic acid compound according to claim 1, which is characterized in that described
Anode electrolytic cell electrode be magnesium sheet electrode, cathode electrode is platinum plate electrode.
7. the synthetic method of polysubstituted allyl carboxylic acid compound according to claim 1, which is characterized in that described
Faradaic current be 5~15mA.
8. the synthetic method of polysubstituted allyl carboxylic acid compound according to claim 1, which is characterized in that described
A concentration of 1mol/L of electric dilute hydrochloric acid.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109518211A (en) * | 2019-01-08 | 2019-03-26 | 合肥工业大学 | A kind of electrochemical method for synthesizing of the even acyl class compound of fragrance |
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| CN101691664A (en) * | 2009-09-30 | 2010-04-07 | 华南理工大学 | Method for synthesizing 3-alkenyl-1, 6-diacid by using electrochemical reaction |
| CN101823958A (en) * | 2009-03-02 | 2010-09-08 | 华东理工大学 | New synthesis method and application of 2-methyl-2-arylpropyl carboxylic ester |
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2018
- 2018-06-13 CN CN201810605790.4A patent/CN108560016A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101823958A (en) * | 2009-03-02 | 2010-09-08 | 华东理工大学 | New synthesis method and application of 2-methyl-2-arylpropyl carboxylic ester |
| CN101691664A (en) * | 2009-09-30 | 2010-04-07 | 华南理工大学 | Method for synthesizing 3-alkenyl-1, 6-diacid by using electrochemical reaction |
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| TONI MORAGAS 等: ""Ligand-Controlled Regiodivergent Ni-Catalyzed Reductive Carboxylation of Allyl Esters with CO2"", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》 * |
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| CN109518211A (en) * | 2019-01-08 | 2019-03-26 | 合肥工业大学 | A kind of electrochemical method for synthesizing of the even acyl class compound of fragrance |
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